Phosphoro sulfenates



United States Patent 3,258,463 PHOSPHORO SULFENATES Glenn R. Price, South Chicago Heights, and Edward N.

Walsh, Chicago Heights, 11]., and James T. Hallett,

Saratoga, Calif., assignors to Stauiler Chemical Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Aug. 29, 1961, Ser. No. 134,590

6 Claims. (Cl. 260-251) This invention is directed to a new class of phosphoruscontaining compounds, their method of preparation and use as herbicides and pesticides.

In particular, the invention relates to phosphoro sulfenates comprising a it =PSOR structure wherein X is oxygen or sulfur. They are selectively active as postand pre-emergence herbicides and also effective in controlling mites, nematodes, aphids and insects of the various common orders.

The new compounds of the invention may be represented by the general formula:

wherein R and R are the same or different alkyl radicals, X is either oxygen or sulfur, and R is a substituted or unsubstituted alkyl, aralkyl, cycloalkyl, alkoxyalkyl, mercaptoalkyl, or heterocyclic radical, or a dialkyl phosphorothio radical selected from the group consisting of those represented by one of the formulae:

RiX RiX wherein X, R, and R as defined above and R, is a phenylene or alkylene which may or may not include an ether or a thio ether linkage.

Suitable substituents for the radicals represented in the general formula by R, are nitro, halo, valkoxy, cy-ano, or phenyl groups and mixtures thereof. The heterocyclic radicals represented by R are those containing one or more atoms of sulfur, oxygen, and/or nitrogen, as for example, furan, thiophene, pyrimidine, pyrrole, pyrazole, imidazole, triazole, oxazole, isothiazole, benzofuran and coumarin. Among the preferred alkyl radicals represented by R, and R of the phosphorus ester portion of the molecule are the methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, and decyl. In general, carbon chains containing not more than 24 carbon atoms have been found satisfactory.

Preparations of the compounds of the present invention is accomplished by reacting a 0,0-dialkyl phosphorosulfenyl halide with a compound having an active OH group (these are represented below by the formula R OH) in the presence of an acid acceptor. The reaction may be represented by the following equation:

l S-Ha1 R OH (acceptor) 3,258,463 Patented June 28, 1966 ICC Generally, the reactions are carried out in a nonaqueous organic solvent to prevent possible side reactions between water and the 0,0-dialkyl phosphorosulfenyl halide. However, some of the sulfenyl halides are comparatively unreactive with water and their reactions are suitably conducted in an aqueous medium. Most of the reactions are mildly exothermic and may be cooled slightly. Reaction temperatures above about C. may cause appreciable decomposition of the reactants, while at temperatures below about 100 C. reaction usually proceeds at a negligibly slow rate. By a preferred method of the invention, a substantially stoichiometric amount of 0,0-dialkylphosphorosulfenyl halide is added slowly to the appropriate reactant (containing an active OH group) which has been dissolved in a solvent together with a tertiary amine while maintaining the reaction temperature within the range of from l00 C. to 100 C. After complete reaction, the crude mixture is filtered and the solvent removed under vacuum.

Compounds of the general formula presented above in which R is a substituted or unsubstituted aryl or alkaryl and R1, R and X are as previously defined, may also be prepared by the method of the present invention. A high degree of pesticidal and herbicidal activity have been found for these compounds bringing them also within the scope of the present invention.

The following examples illustrate specific compounds prepared by the method of the present invention:

Example 1 P SO ozHs cz s In a flask was placed 15.9 grams of C I-I SC H OH and 15.1 grams of triethylamine in 150 ml. of ether. The solution was cooled to 10 C. and 30.5 grams of (C I-I O) P(O)SCl was added over a 60 minute period. After the crude reaction mixture was filtered and the solvent removed under partial pressure, the product was stabilized by heating to 50 C. at 1 mm. of Hg. The yield was 36.0 grams of (C H O) P(-O)SOC H SC H having an index of refraction N =1.4820 and analyzing 10.9% P and 22.0% S as compared to 11.3% P and 23.4% S theoretical.

Example 2 To a solution of 32.8 grams of BrCI-I CH(OH)CH Br and 15.1 grams of triethylamine in 75 ml. of ether was added 30.5 grams of (C H O) P(O)SO1 over a 30 minute period at 10 C. The reaction mixture was stirred for an additional hour at room temperature and then filtered. After removing the solvent under partial pressure, the product was stabilized to 50 C. at 1.0 mm. of Hg. The yield was 55.5 grams of (C2H50) 2P 2 having an index of refraction N =L5026 and analyzing as 7.3% P, 7.7% S, and 41.2% Br compared to 7.9% P, 8.3% S, and 41.5% Br theoretical.

Example 3 Using the process described above, 21.8 grams of BrCH CH(OH)OH Br was treated with 37.3 grams of (C H O) P(O)SCl in the presence of triethylamine to yield 49.0 grams of (C3H17O)2P(O) SOCH(C-H Br) having an index of refraction N =1.4852 and analyzing as 5.5% P, 5.5% S, and 27.8% Br compared to 5.6% P, 5.7% S, and 28.9% Br theoretical.

Example 4 P-SOCH Using the process described above, 16.3 grams of HOCH(CH Br) was treated with 21.6 grams of '(C H O) (C H O)P(O)SCl in the presence of 7.6 grams of triethylamine to yield 35.0 grams of (C H O) (C H O)P(O)SOCH (CH Br) was treated with 33.0 grams of (C H O) P(S) SCl in the presence of 15.1 grams of triethylamine giving 61.0 grams of (C H O) P(S)SOCH(CH Br) having an index of refraction N =1.5230 and analyzing as 7.5% P, 14.5% S and 39.7% Br compared to 7.7% P, 15.9% S, and 39.8% Br theoretical.

CHzBr Example 6 P-SOCH2O0 1 To a solution of 15.1 grams of triethylamine in 75 ml.

of ether was added a mixture of 22.4 grams of HOCH CCL, and 30.4 grams of (C H O) 'P(O)SCl over a 30 minute period at 10 C. After the reaction mixture had stirred for 30 more minutes at room temperature, it was filtered and the solvent was removed under partial pressure. The product was stabilized by heating to 50 C. at 1.0 mm. Hg to yield 44.5 grams of (C H O) P(O) SOOH CCl having an index of refraction N =l.47'82 and analyzing as 9.0% P, 9.5% S, and 31.2% C1 compared to 9.7% P, 10.1% S and 33.6% C1 theoretical.

Example 7 H5ozo\( P-SH@ sCaO To a solution of 15.5 grams of triethylamine and 16.2

grams of C H CH OH in 75 ml. of ether was added 30.4 grams of (C H O) P(O)SCl over a 30 minute period at C. After the crude product 'was stirred for an additional 30 minutes, the reaction mixture was filtered and the solvent removed under partial pressure. The reaction mixture was stabilized to 50 C. at 1.0 mm. Hg to yield 40.5 grams of (C H O) P(O)SOOH C H having an index of refraction N =1.5042 and analyzing as 10.4% P and 10.9% S compared to 11.2% P and 11.6% S theoretical.

Example 8 To a solution of 19.2 grams of p-chlorophenol and 15.3 grams of t-riethylamine in 75 ml. of ether was added 30.5 grams of (C H 0)gP(O)SCl over a 30 minute period at 10 C. After the reaction mixture was stirred for an additional 60 minutes, it was filtered and the solvent was evaporated under partial pressure. The reaction product was stabilized to 50 C. at 1.0 mm. Hg to yield 47.0 grams of (C H O) P(O)SOC H Cl having an index of refraction N =1.5128 and analyzing as 9.4% P, 9.7% S and 11.7% C1, compared to 10.4% P. 10.6% S, and 12.0% C1 theoretical.

Example 9 To a solution of 25.5 grams of p-phenyl phenol and 30.5 grams of (C H O) P(O)SCl in ml. of ether was added 15.2 grams of triethylamine at 10 C. over a 30 minute period. After the reaction mixture had stirred for an additional 60 minutes, it was filtered and the solvent was removed under partial pressure. The reaction product was stabilized to 5 0 C. at 1.0 mm. Hg to yield 50.0 grams of (C H O) P(O)SOC H C H analyzing as 8.8% P and 8.2% S compared to 9.1% P and 9.5% S theoretical.

Example 10 To a solution of 2-(isopropyl)-4-(methyl)-6-('hydroxy) pyrimidine in 250 of benzene was added 30.5 grams of (C H O) P(O)SCl. The solution was cooled to 20 C. and 15.1 grams of triethylamine was added over a 30 minute period. After the reaction mixture was allowed to stir for another hour at room temperature, it was filtered and the solvent evaporated under partial pressure. The product was dried over P 0 at 1.0 mm. of Hg to yield 46.0 grams of N =1.4782; yield=94.5%; percent P=9.0 (9.8 theory); percent S=16.7 (17.1 theory).

5 Example 14 B 0\lel. /OH Br P-SO-CH H360 CI'IZBI N =1.5259; yie1d=100.0%; percent P=8.0 (8.3 theory); percent S=16.7 (17.1 theory).

Example 15 PSO02H4O02H40 C4119 H5020 N :1.4494; yie1d=98.0%; percent P=9.0 (9.4 theory); percent S=9.1 (9.7 theory).

Example 16 PSOCH2CHB1CH2B1 H5020 N =1.5058; yie1d=95.0%; percent P=7.8 (8.0 theory); percent S=7.1 (8.3 theory).

Example 17 H5020 fi \PSOOCH3 H5020 N =1.5060; yie1d=98.0%; percent P=9.6 (10.6 theory); percent S=9.4 (10.9 theory).

Example 18 t -SOQCH N =1.5006; yield: 100%; per-cent P=10.1 (11.2 theory); percent S=10.0 (11.5 theory).

Example 20 Yie1d=99.0%; percent P=8.1 (7.2 theory); percent S=7.3 (7.3 theory).

Example 21 C1 C1 H17Cs0\fi PS O C1 Yield=88.0%; percent P=5.15 (5.15 theory); percent S=4.8 (5.3 theory).

Example 22 N =1.4761; y|ield=99.0%; percent P=6.9 (6.0 theory); percent S=5.7 (6.2 theory).

6 Example 23 ND25='1.5569; yield=89%; percent P=6.92 (6.9 theory); percent S=14.9 (14.2 theory).

Example 24 C1 01 H300 S PSO NF: 1.5730; yield:

Example 25 Yield=87%; percent P=8.0 (7.7 theory); percent 8:82 (7.95 theory).

Example 26 N =l.5230; yie1d:100%; percent P=9.6 (10.2 theory); percent 8: 9.8 (10.9 theory).

Example 27 Br 5C2O\IO| PSO- N02 c H6020 Yie1d=100%.

Example 28 N =1.4999; percent P=10.6 (11.8 theory); percent S=10.4 (12.1 theory).

Example 29 H5020 0 0 0C2H5 H5020 OCgHs N =1.495O; percent P=13.1 (13.8 theory); percent S=14.0 (14.3 theory).

Example 31 H5020 o s OCzH N =1.5114; percent P=12.8 (14.0 theory) percent S=25.0 (28.8 theory). p V

7 8 Example 32 The following pest species were used in both screening and bioassay tests: E5020 (1) House fly-Musca domestica (Linn.).

g (2) American cockroachPeriplaneta americana (Linn.). \S/ (3) Spotted milkweed bug0nc0peltus fasciatus (Dal- HaCzO 1 N =1.54l8; percent P=10.3 (9.75 theory); percent (4) Confused flour beetle-Tribolium confusum (Duvol). S=18.3 (20.1 theory). (5) Two-spotted miteTetranychus Ielarius (Linn.).

Example 33 (6) Salt-marsh caterpillar Estigmene acrea (Drury). H C O O 10 In the screenmg tests for insects numbered 1 to 4 above, 5 2 \H from ten to twenty-five insects were caged in cardboard mailing tubes 3 /3" in diameter and 2 /2" tall. The cages H5020 were supplied within cellophane .bottoms and screened tops. Food and water were supplied to each cage, except 1r 25 0 1n the case of the confused flour beetle wh1ch was pri- ND :154875 Percent P=9-0 theory) Pfircent marily tested to determine fumigant action. Dispersions 5:97 (lo-3 theory)' of the test compounds were prepared by dissolving one Example 34 half gram of the toxic material in ten milliliters of ace- HSCQO 0 tone. This solution was then diluted with water containing 0.015% Vatsol (a sulfonate-type wetting agent) and PSO 0:0 0.005% methocel (methyl cellulose) as emulsifiers, the H5020 6 amount of water being sufiicient to dilute the active ingredient to a concentration of 0.1% or below. The test insects were then sprayed with this solution. After twenty-four and seventy-two hours, counts were made to Percent P=8.41 (9.0 theory); percent S=8.60 (9.20 determine living and dead insects. theory Compounds which showed high mortality of house flies Ex mpl 35 in the screening test were bioassayed on M. domestica. H5020 O /N 30 In this test, a known quantity of the toxicant was placed \ll in a confined area so that it was possible to calculate the P- s 0- N02 exact amount of toxlcant per fly. For the fly bioassay, H5020 the same cages were employed as for the screemng tests. The toxicant was placed in a 60 mm. diameter petri dish Percent y); Percellt 5:97 (lo-3 along with 1 ml. of acetone containing light spray oil. theory)- After the solution air dried, a cage containing twenty-five Example 36 female flies was placed over the residue. Counts of liv- 0 ing and dead insects were made after twenty-four and seventy-two hours.

E5020 0 40 Essentially the same procedure was followed in the confused flour beetle bioassay as in the house fly bioassay. G For thlS test, however, twenty adult beetles were used. H5 20 Mortality was checked at twenty-four and forty-eight ll hours.

The miticidal screening test involved using young Pinto Percent P=8.9 (8.9 theory); percent S=8.1 (9.25 bean plants in the primary leaf stage as host plants for theory). the mites. The beam plants were infested with several Pestioidal activity for the compounds of the foregoing hundred mites and then sprayed to run-off with an aqueexamples is illustrated in Table I wherein the percentage ous test suspension prepared as described above. Sprayed kill is reported for a specified quantity of toxicant eX- plants were transferred to a greenhouse and held for fourpressed in micrograms (hereafter termed the bioassay teen days. The miticidal and ovicidal activity of the test test) or for a percentage concentration of toxicant in compounds were determined after seven and fourteen aqueous solution (hereafter termed the screening test). days. The fourteen day reading was necessary for evalu- A slanted line [is used to separate the percentage kill, shown ating ovicidal action. Percentage mortality is reported, on the left, and the percentage concentration or quantity, as shown in Table I, supra, for both post-embryonic and shown on the right. embryonic forms.

TABLE I House American Milkweed Confused Two-spotted Two-spotted Salt-marsh Example Flies Roach, Bug, Flour Mite Post; Mite-eggs, Caterpillar,

percent percent Beetle emb., percent percent percent 100/01% 100/01 100/0. 05 100/O.1% 10010.05 100/012 0/01 96/0.1% 20/01 40/01 loo/501 90/012 90/012 100/50;tg 40/01 100/0. 05 100/50 g.-- 00/012 90/012 loo/50 80/0. 05 100/50 g-.. 50/0. 12 25/012 92/50,. /0. 1 100/50yg 00/0. 12 00/0. 12 /0. 01 100/50,. /0. 12 0/0. 12 30/0. 01 IOU/50 g.-- 30/0. 1 0/0. 1% 95/012 90/0 12 100/50 g /0. 05 100/0.1 100/50,. 00/012 25/012 12/10,. 100/01 100/01 100/01% 50/0. 12 25/012 100/50 g... 100/01 /0. 025 15/10,. 50/012 0/012 92/50,. 80/0.1 /0. 05 100/50,. 198/812 12 80/0. 1%-.. 0/0. 1 30/0 05 0/0. 1%.--- 100/0 12 50/0 12 100/50pg--- 100/01 100/01 100/10,. 50/0. 12 25/012 100/50,. 100/01 70/001 100/0. 1%-- 0/01 0/01 100/0. 1%.- 40/01 0/01 loo/01%-- 90/012 50/012 100/0. 1%-- 50/01 0/01 100/0. 1%-- 100/012 100/012 100/0. 05 100/0. 05 75/0. 01 0/0. 01

9 it) Lepidopterous evaluation test.--The test organism is sprayed on the pre-planted soil. After 14 days the plants the salt-marsh caterpillar, species No. 6 above, a reprewere inspected and compared with an untreated control sentative member of an order containing a large number group planted on the same day. The usual plant species of economically important plant pests. Test solution of employed in this test were crabgrass, foxtail, watergr ass, various concentrations were prepared by dissolving the wild oats, pigweed, mustard, and dock.

active material in stock solutions of water containing Post-emergence herbicidal tests were initiated approxiwetting agents by the procedure outlined heretofore. mately two weeks following emergence of the test plants. Dock leaves approximately five inches long were dipped The method of application involved spraying on the plant in these solutions for ten seconds. The leaves were then foliage a 0.2% aqueous solutionof the active compound allowed to dry. A filter paper disk Was placed in a one to the point of run-off. The concentration of active mapound food container and moistened with one ml. of terial at this point was approximately 25 pounds per water. The dried dock leaves were then introduced into planted acre. The usual plant species employed in postthe container together with five third instar salt-marsh emergence herbicidal testing were annual bluegrass, bindlarvae. A petri dish cover was used for convenient ob- Weed, fox musta d, wild oats and pinto bean. Evaluservation, The t t ere du t d f forty-eight ation of herbicidal activity was accomplished after 14 to hours. After twenty-four hours a fresh, undipped dock 9 ys.

leaf was placed in the container. Mortality readings o g t e specific examples show the use of aqueous w t k t twenty-four d forty-eight h solutions of the toxic compounds as insecticides and Th compounds of th present invention were l herbicides, they may also be used in the form of emulsions,

tested for herbicidal activity on some economically imnon'aqueous Solutions, Wettable P p and portant plant species. The data obtained from such tests dusts as y best S 11ite d t0 the Conditions 11S6- are reported in Table 11 wherein 0 indicates no more specialized applications, the toxic material may even preciable herbicidal activity, is slight injury, be used 111 P3 5 q is moderate injury, and is Severe injury to plant The term pest 1s used herein 1n the restrlcted sense life. The following reference characters are used in generally Pecogmzed U art as applymg tofhe lower Table H to represent the indicated plant Species: forms of life customarily controlled by chemlcal means and excluding the higher animals, the vertebrates, e.g., Al=a nlluail bluegrass rodents, birds, and larger forms, which are more com- B=blndweed monly controlled by mechanical means such as traps. In C=CIB gIa its broadest usage, the term refers to both the destructive D=dock or annoying household or plant pest organisms, especially E=watergrass the parasites and pathogens. It will be apparent to one F=foxta1l I skilled in the art that the toxic activity demonstrated on G=p1gweed the selected arthropods, arachnids, and lepidopterous H= radrsh larvae is indicative of toxic activity in various species and J= 1mson weed orders not specifically shown. M=mustard The foregoing description is given for clearance of N= t (tame) understanding only and no unnecessary limitations should O=0ats (w1ld) be understood therefrom, as modifications will be obvious P=pinto bean to those skilled in the art.

TABLE II Example Mode of Application A B C D E F G I H .T M N O 1? (Compound) 2 Post-emergence..." O 0 0 0 0 e do 0 o 0 0 o 6 Pre-emergence 0 0 0 0 S. I

Ge. Ge. 10 "do"-.. 0 11 Iost-emergence 0 0 0 0 O .do.- 0 0 0 0 0 ao E' De. De. De. De. Pre-emergence g Post-emergence-.... g++ 0 0 e. e. Pre-emcrgence 0 G. l? t- Pt2 ;ti%3. 0 i +F iii O..

Post-emergence 0 29 Fire-emergence 0 0 De- 30 Post-emergence 0 0 0 0 T. D.

as. I. represents shortened intermode; Ge. represents germination; L. M. represents leaf malformation; De. represents desiccation; T. D. represents tip ea To more specifically define the type of activity ob- What we claim is: served, where substantial plant injury resulted, super- 1. Acompound represented by the general formula: scripts, such as S. 1., Ge. etc., are shown in Table II. R10 X Pre-emergence herbicidal tests were conducted folloW- \H ing planting, but prior to emergence of the plants, usually PTS O R the day following planting. The active compounds were R20 applied at a Concentration of 20 of active material, wherein R and R are alkyl radicals, X is selected from diluted in Wale! to 3 Volume of 30 gallons, for each acre the group consisting of sulfur and oxygen and R is selected treated. The aqueous herbicidal solution was simply from the group consisting of unsubstituted lower alkyl,

1 1 bromo substituted lower alkyl, chloro substituted lower alkyl, benzyl, cyclohexyl, lower alkoXy-lower alkyl, ethylmercaptoethyl, pyridyl, coumarinyl, benzthiazyl, pyrimidyl, naphthyl, phthalimidomethylene, and dialkyl phosphorothio radicals represented by one of the formulae:

wherein X, R and R are as defined above and R is selected from the group consisting of lower alkylene, phenylene, lower alkylene ether, and lower alkylene thio ether.

2. The compound of the following formula:

H5Cz0 O PS0C H20 01 H50 20 3. The compound of the following formula:

\ u i J P s o o H N 3 H5020 4. The compound of the following formula:

HsCzO O .1 2 5. The compound of the following formula:

HaCzO 0 i soozulo 021140 0411,,

6. The compound of the following formula:

H5020 O S H5020 OCzHa References Cited by the Examiner OTHER REFERENCES Lowy et 211., Introduction to Organic Chemistry, Seventh Edition (1951), pages 215-6.

HENRY R. JILES, Acting Primary Examiner. NICHOLAS S. RIZZO, Examiner. 

1. A COMPOUND REPRESENTED BY THE GENERAL FORMULA: 